SYSTEM COMPRISING RELEASE AGENT AND HIGH PEEL ADHESION REPOSITIONABLE ADHESIVE

Abstract: The present invention is a system comprising a high peel adhesion repositionable system and release agent. The high peel adhesion repositionable system comprises microspheres and a binder including at least one acrylamide moiety. The release agent comprises a polymer having at least one vinyl polymeric segment having a Tg between -10 DEG C and 65 DEG C and at least one siloxane polymeric segment.

Description: SYSTEM COMPRISING RELEASE AGENT AND HIGH PEEL ADHESION REPOSITIONABLE ADHESIVE FIELD OF INVENTION The present invention relates to repositionable adhesives. In particular, the present invention relates to high peel adhesion repositionable adhesives and a release agent. BACKGROUND OF THE INVENTION Adhesives can be utilized to make products such as tapes, labels, note tablets and various adhesive coated sheets by coating an adhesive onto a backing or substrate. These adhesive products must be protected from unintended adhesion to other surfaces. Hence, tapes are typically wound into a roll on their own backing. In order to allow the roll to be unwound without undesirable transfer of adhesive to tape backing, it is customary to provide the tape backing with a low adhesion backsize. The release agent must reproducibly provide an appropriate level of release to the adhesive of interest, but not to deleteriously affect the adhesive. Moreover, the release coating should not impair the writing quality or indicia receptibility of the substrate. Typically, positionable adhesives are utilized with release agents. Positionable adhesives are those which allow for the placement of an article containing such adhesive onto a receptor in an exact position, because the article can be adjusted relative to the receptor after initial placement. In some instances, the adhesive can be designated repositionable or repeatedly reusable. As used herein, the term "repositionable" refers to the ability to be repeatedly adhered to and removed from a substrate without substantial loss of adhesion capability. Such adhesives exhibit aggressive tack but low peel adhesion properties, thus allowing repeated reusability. It is often desirable to utilize repositionable adhesives having higher peel adhesions than those obtained with conventional repositionable adhesives. Moreover, it is desirable that the repositionable adhesive does not build adhesion excessively with time. Generally, systems in the art provide one of the following: i.) low-peel adhesion with an indicia receptive surface; ii.) high peel adhesives which exhibit increasing peel adhesion with prolonged attachment and a reduced indicia receptivity; and high peel adhesives which exhibit increasing peel adehsion with prolong attachment an with unacceptably high release force. It has now been found that a repositionable adhesive composition having high peel adhesion can be contacted with an indicia receptive release agent and yet be removed from the release agent without any deleterious effects. This adhesive composition comprises an adhesive blend including microspheres and a binder, preferably, comprising at least one acrylamide moiety. SUMMARY OF THE INVENTION The present invention includes an adhesive composition comprising a blend of one or more microspheres and an adhesive binder comprising at least one acrylamide-based moiety and a release agent comprising a polymer having at least one vinyl polymeric segment having a T g between -10°C and 65°C and at least one siloxane polymeric segment. Preferably, the microspheres of the present invention are polymeric, inherently tacky and elastomeric. The binder which preferably has pressure sensitive adhesive properties comprises a polymer having at least one acrylamide-moiety. If desired, the acrylamide-moiety can be copolymerized with free radical polymerizable monomers. The release agent of the present invention is coated onto a first substrate such as a paper backing. The agent comprises a polymer having at least one vinyl polymeric segment having a T g between -10°C and 65°C and at least one siloxane polymeric segment. Preferably, the T g should be between 20°C and 45°C of the vinyl polymer segment. In one embodiment of the present invention, the release agent is a copolymer which comprises the formula: wherein R, are monovalent moieties which can independently be the same or different and are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fluoroalkyl; R 2 can independently be the same or different and are divalent linking groups; R 3 are monovalent moieties which can independently be the same or different and are selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fluoroalkyl; R_. can independently be the same or different and are divalent linking groups; x is an integer of 0-3; y is an integer of 10 or greater; q is an integer of 0-3; G 5 and G 6 are monovalent moieties which can independently be the same or different selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is a divalent linking group and A is defined below; and G 2 and G 4 comprise A wherein A is a vinyl polymeric segment or block consisting essentially of a polymerized free radically polymerized monomer. In another embodiment of the present invention, the release agent comprises a copolymer of D and E monomers copolymerized to form a polymeric backbone with F monomer grafted thereto wherein: D is at least one free radically polymerizable vinyl monomer; E is at least one polar monomer copolymerizable with D, the amount of E being up to 30% of the total weight of all monomers, and F is a monomer having the general formula wherein X is a vinyl group copolymerizable with the D and E monomers, Y is a divalent linking group where n is zero or 1; m is an integer of 1 to 3; R is hydrogen, lower alkyl (e.g., methyl, ethyl, or propyl) , aryl (e.g., phenyl or substituted phenyl) , or alkoxy groups; and Z is a monovalent siloxane polymeric moiety having a number average molecular weight above about 1,000 and is essentially unreactive under copolymerization conditions. The present invention also includes an article comprising at least two substrates with front and rear surfaces. The first substrate should have at least a portion of its rear surface coated with the adhesive composition of the present invention and the second substrate should have at least a portion of its front surface coated with the release agent of the present invention. The adhesive composition must contact the release agent when the substrates are stacked or rolled. The article can have additional substrates between the first and second substrates. Each additional substrate should have at least a portion of its rear surface coated with the adhesive composition and a portion of its front surface coated with the release agent. The following terms have these meanings as used herein: 1. The term "droplet" means the liquid stage of the microspheres prior to the completion of polymerization. 2. The term "cavity" means a space within the walls of a droplet or microsphere when still in the suspension or dispersion medium prior to drying, and thus containing whatever medium was used. 3. The term "void" means empty space completely within the walls of a polymerized microsphere. All weights, parts and ratios herein are by weight unless specifically stated otherwise. DETAILED DESCRIPTION OF THE INVENTION The microspheres of the present invention should be polymeric and elastomeric. Preferably, the microspheres are inherently tacky and solid although hollow microspheres can be utilized. The microspheres should comprise at least one alkyl acrylate or alkyl methacrylate ester. Alkyl acrylate or methacrylate monomers useful in preparing the solid microspheres for pressure-sensitive adhesives of this invention are those monofunctional unsaturated acrylate or methacrylate esters of non-tertiary alkyl alcohols, the alkyl groups of which have from 4 to 14 carbon atoms. Such acrylates are oleophilic, water emulsifiable, have restricted water solubility and as homopolymers, generally have a glass transition temperature below about -20°C. Included within this class of monomers are, for example, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate and the like, singly or in mixtures. Preferred acrylates include isooctyl acrylate, isononyl acrylate, isoamyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, sec-butyl acrylate and mixtures thereof. Acrylate or methacrylate or other vinyl monomers which, as homopolymers, have glass transition temperatures higher than about -20°C, e.g., tert-butyl acrylate, isobornyl acrylate, butyl methacrylate, vinyl acetate, N-vinyl pyrolidone, acrylamide and the like may be utilized in conjunction with one or more of the acrylate or methacrylate monomers provided that the glass transition temperature of the resultant polymer is below about -20°C. Preferred microspheres are described in U.S. Patent No. 3,691,140 which is herein incorporated by reference. These microspheres utilize at least one monomer selected from the group consisting of substantially oil-insoluble, water soluble, ionic monomers and maleic anhydride. The monomers can be utilized alone, as a mixture of two or more ionic monomers or as a mixture of maleic anhydride and one or more ionic monomers. Examples of ionic monomers include, but are not limited to, sodium methacrylate, ammonium acrylate, sodium acrylate, trimethylamine p- vinyl benzimide, 4,4,9-tri-methyl-4-azonia-7-oxo-8-oxa- dec-9-ene-l-sulphonate, N,N-dimethyl-(/3- methacyloxoxyethyl) ammonium propionate betaine, trimethyla ine methacrylamide. Microspheres can be prepared by an aqueous suspension polymerization technique utilizing emulsifiers in an amount greater than the critical micelle concentration. Critical micelle concentration is defined as that minimum emulsifier concentration necessary for the formation of micelles. The critical micelle concentration is slightly different for each emulsifier. Useable concentrations typically range from about 1.0 X 10 to about 3.0 moles per liter. Anionic, nonionic or cationic emulsifiers can be used. Typical examples of anionic emulsifiers include sodium dodecylbenzene sulfonate, sodium salts of alkyl aryl ether sulfonates and the like. Examples of nonionic emulsifiers include ethoxylated oleyl alcohol and polyoxyethylene octylphenyl ether and a useful cationic surfactant is a mixture of alkyl dimethylbenzyl ammonium chlorides wherein the alkyl chain is from ten to eighteen carbons long. While only examples of anionic, nonionic and cationic emulsifiers are given herein, it is believed that amphoteric emulsifiers would likewise work. Initiators effecting polymerization are those which are normally suitable for free-radical polymerization of acrylate monomers. Examples of such initiators include thermally-activated initiators such as azo compounds, hydroperoxides, peroxides and the like and photoinitiators such as benzophenone, benzoin ethyl ether and 2,2,-dimethoxy-2-phenyl acetophone. Other suitable initiators include lauryl peroxide and bis(t-t-butyl cyclohexyl)peroxy dicarbonate. The initiator concentration should be sufficient to bring about a complete monomer conversion in a desired time span and temperature range. Parameters which affect the concentration of initiator employed include the type of initiator and particular monomer and/or monomers involved. It is believed that effective concentrations range from about 0.10 to about 1 percent by weight of the total monomers and more preferably, from about 0.25 to about 0.70 percent by weight monomers and/or monomers. Polymeric stabilizers may also be present, but are not necessary. Upon addition, heat or radiation are applied to initiate the polymerization of the monomers which is an exothermic reaction. The microsphere composition may also contain a crosslinking agent. Examples of useful crosslinking agents include, but are not limited to: multifunctional (meth)acrylate(s) , e.g., butanediol diacrylate or hexanediol diacrylate or other multifunctional crosslinkers such as divinylbenzene and mixtures thereof. When used, crosslinker(s) is (are) added at a level of up to about 0.15 equivalent weight percent, preferably up to about 0.1 equivalent weight percent, of the total polymerizable composition. The "equivalent weight percent" of a given compound is defined as the number of equivalents of that compound divided by the number of equivalents in the total composition, wherein the equivalent is the number of grams divided by the equivalent weight. Following polymerization, a stable aqueous suspension of solid microspheres at room temperature is obtained. The suspension may have non-volatile solids contents from about 10 to about 50 percent by weight. Upon prolonged standing, the suspension separates into two phases, one being aqueous and the other being an aqueous suspension of the polymeric sphere. The aqueous suspension of microspheres may be utilized immediately following polymerization, because the suspension is stable to agglomeration or coagulation, under room temperature conditions. Decantation of the microsphere-rich phase provides an aqueous suspension having a non-volatile solids content, which if shaken, will readily redisperse. Alternatively, the suspension may be coagulated with an organic liquid such as methanol, followed by washing and drying. These partially dried polymer spheres, with sufficient agitation, will readily suspend in a variety of common organic solvents such as ethyl acetate, tetrahydrofuran, heptane, 2-butanone, benzene cyclohexane and esters. Suitable binders include polymers having at least one acrylamide-based moiety. The acrylamides which can be used in the present invention are the reaction products of an acrylic or ethacrylic acid with ammonia or primary or secondary amines. Examples of suitable acrylamides include, but are not limited to, acrylamide, isooctyl acrylamide, 2-ethyl hexyl acrylamide, and N,N-dimethyl acrylamide. If desired, the acrylamides can be copolymerized with one or more monomers having vinyl groups. Any vinyl monomer may be used so long as the product acts as a binder for the microspheres and does not deleteriously inhibit the release agent and adhesive. Suitable monomers include alkyl acrylates or methacrylates. Alkyl acrylate or methacrylate monomers useful in preparing the binder are those monofunctional unsaturated acrylate or methacrylate esters of non-tertiary alkyl alcohols, the alkyl groups of which have from 4 to 14 carbon atoms. Examples of such monomers include esters of acrylic acid or methacrylic acid with non-tertiary alkyl alcohols such as 1- butanol, 1-pentanol, 2-methyl-l-butanol, 1-methyl-l- butanol, 1-methyl-l-pentanol, 2-methyl-1-pentanol, 3- methyl-1-pentanol, 2-ethyl-l-butanol, 3,5,5-trimethyl- 1-hexanol, 3-heptanol, 2-octanol, 1-decanol, 1- dodecanol, isooctyl alcohol, isononyl alcohol, 2-ethyl- hexyl alcohol and the like. Such monomeric acrylic or methacrylic esters are known in the art and many are commercially available. Preferably, the binder comprises up to about 15 parts acrylamide and from about 85 to about 100 parts by weight acrylic or methacrylic ester. More preferably, the binder comprises from about 4 to about 10 parts acrylamide and from about 91 to about 96 parts acrylic or methacrylic ester. The adhesive composition of this invention is made by combining the binder with the microspheres. If an organic dispersion of the adhesive is desired, a solution of binder is combined with an organic dispersion of microspheres. If an aqueous adhesive composition is desired, an aqueous suspension of microspheres is combined with an aqueous solution of binder. Preferably, the weight of the binder comprises from about 10 to about 90 parts by weight of the adhesive and the microspheres comprise from about 10 to about 90 parts by weight of adhesive of this invention. Properties of the repositionable pressure- sensitive adhesives of the present invention can be altered by the addition of a tackifying resin(s) and/or plasticizer(s) . Preferred tackifiers for use herein include hydrogenated rosin esters commercially available from such companies as Hercules, Inc. under the tradenames Foral™ and Pentalyri™. Individual tackifiers include those based on t-butyl styrene. Useful plasticizers include dioctyl phthalate, 2-ethyl hexyl phosphate, tricresyl phosphate and the like. Optionally, colorants, fillers, stabilizers and various other polymeric additives can be utilized. Preferably, the repositionable adhesive compositions of the present invention should have a peel adhesion of at least about 125 g/1.25 inches. (3.88 N/dm) . More preferably, the peel adhesion should be at least 250 g/1.25 inches. (7.76 N/dm). The present invention also includes a release agent which is capable of releasing a repositionable adhesive having high peel adhesion. The release agent has at least one siloxane polymeric segment and at least one vinyl polymeric segment having a T g between - 10°C and 65°C. By virtue of its chemical composition and structure and the resultant properties, the release agent is well-suited for repositionable adhesives having higher peel adhesions. In one embodiment of the present invention, the release agent is a copolymer which comprises the formula: R, are monovalent moieties which can independently be the same or different which are selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen. Preferably, R, are monovalent moieties which can independently be the same or different selected from the group consisting of C M alkyl and hydroxyl. Most preferably, R, is selected from the group consisting of methyl and butyl. R 2 are divalent linking groups which can independently be the same or different. Suitable divalent linking groups include but are not limited to the following: C, to C 10 alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably, R 2 is selected from the group consisting of Cj. 3 alkylene and C 7 -C 10 alkylarylene due to ease of synthesis of the compound. Most preferably, R 2 is selected from the group consisting of -CH 2 -; 1,3-propylene; and R 3 are monovalent moieties which can independently be the same or different which are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl and fluoroalkyl, and hydrogen. Preferably, R 3 are monovalent moieties which can independently be the same or different selected from the group consisting of C M alkyl and hydroxyl. Most preferably, R 3 is selected from the group consisting of methyl and butyl. R, can independently be the same or different. Suitable divalent linking groups include but are not limited to the following: C, to C 10 alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably, R, is selected from the group consisting of C,. 3 alkylene and C 7 -Cj 0 alkylarylene for reasons of case of synthesis. Most preferably, R, is selected from the group consisting of -CH 2 -; 1,3-propylene; and G 5 and G 6 are monovalent moieties which can independently be the same or different selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is a divalent linking group and A is defined below. W are divalent linking groups. Suitable divalent linking groups include, but are not limited to, C 1 to C J Q alkylene, alkarylene, arylene, and alkoxyalkylene. Preferably, W is selected from the group consisting of methylene and propylene. G 2 and G 4 comprise A. A is a vinyl polymeric segment consisting essentially of polymerized free radically polymerizable monomer. A can comprise either a homopolymer segment or block or a copolymer segment or block. The substrate anchorage properties of the release agent are determined by the vinyl polymeric segment content. The chemical nature or composition of the vinyl polymeric segments can be modified to improve substrate anchorage and adhesion to the substrate. Thus, the release agent can be chemically tailored to provide a specific level of substrate anchorage. The selection of the composition of A is typically based upon the intended use of the release agent and the properties the release agent must possess in order to accomplish its intended purpose. A can include, but is not limited to, those monomers wherein the free radically polymerizable monomer or monomers are chosen such that a vinyl segment has a T g or T m above about -20°C. The preferred free radically polymerizable monomers are selected from the group consisting of N-vinyl pyrrolidone, N,N- diethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N- dimethylaminoethyl acrylate and N-t-butylamino ethyl methacrylate, styrene, methyl methacrylate, methyl acrylate, acrylic acid, Ataconic acid, maleic acid, 2- carboxy ethyl acrylate, acrylamide, methacrylamide, acrylonitrile, isobornyl methacrylate, , butyl methacrylate, isopropyl methacrylate, vinyl acetate, hydroxy propylacrylate, hydroxy ethyl acrylate, dihydroxy propyl acrylate and mixtures thereof. The amount and composition of the vinylic segment to silicone should range from about 98 to about 2 parts to about 40 to about 60 parts by weight. Preferably, the vinyl polymeric segments should have a molecular weight in the range of 2,000 to 80,000, preferably 5,000 to 50,000. The release properties of the agent are determined by both the silicone content (weight percentage) of the copolymer and the molecular weight of the silicone segment, with higher silicone content and/or molecular weight providing easier release. A copolymer or copolymer blend can, therefore, be chemically tailored to provide a specific level of release which can be reproduced with consistency, thus making possible the variation of the release properties of a liner over a range of values in a controlled fashion. The silicone polymeric segment must have an average molecular weight above about 1000 in order for the release agent to function properly. Preferably, the silicone polymeric segment has a number average molecular weight of about 1000 to about 20,000. Most preferably, the silicone polymeric segment has a number average molecular weight ranging from about 2,000 to about 15,000. The silicone polymeric segment can comprise about 2 to 60 wt% of the release agent in order to allow for a wide range of release performance. In another embodiment of the present invention, the release agent comprises a copolymer of D and E monomers copolymerized to form a polymeric backbone. Grafted to the backbone is an F monomer. The D and E monomers provide the adhesion to the substrate and other properties such as ink receptivity and water solubility. The F monomer provides the release properties. The D monomer or monomers (there may be more than one) are chosen such that the backbone T g or T m is above about -20°C. Representative examples of D monomers include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile and acrylic or methacrylic acid esters of nontertiary alcohols or tertiary alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclohexanol, benzyl alcohol, dodecanol, hexadecanol, and octadecanol, the alcohols having from 1 to 18 carbon atoms. Especially preferred D monomers include methyl methacrylate, butyl methacrylate, vinyl acetate, partially hydrolyzed vinyl acetate, methyl acrylate and octadecyl acrylate. Representative E monomers useful in practicing the invention, and which may be used either individually or in combination, include carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and 2-carboxyethyl acrylate and their ammonium or metal salts; sulfonic or phosphonic acids such as 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, styrene sulfonic acid, and vinyl benzyl phosphonic acid and their ammonium or metal salts; amides such as acrylamide, methacrylamide, N,N-dimethyl acrylamide, and N-vinyl pyrrolidone, N,N-diethylaminoethyl methacrylate, N,N- dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate and N-t- butylamino ethyl methacrylate; and monomers having hydroxyl functionality (e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, and dihydroxypropyl acrylate) , ammonium functionality derived from reaction of amine-containing monomers (e.g., N,N,-dimethylaminoethyl methacrylate and vinyl pyridine) with alkylating agents or protic acids, or zwitterionic functionality such as that derived by reaction of amine monomers with hydrogen peroxide or propane sulfone. The F monomer has the general formula: X~( Y )nSlR( 3 -m)Z m X is a vinyl group copolymerizable with the D and E monomers. The preferred F monomer may be further defined as having an X group which has the general formula: R 1 R 2 I I CH=C— wherein R 1 is a hydrogen atom or a COOH group and R 2 is a hydrogen atom, a methyl group, or a CH 2 COOH group. The Z group of the F monomer has the general formula: where R 3 and R 5 are independently lower alkyl, aryl, or fluoroalkyl, where lower alkyl and fluoroalkyl both refer to alkyl groups having from one to three carbon atoms and where aryl refers to phenyl or substituted phenyl. R 4 may be alkyl, alkoxy, alkylamino, aryl, hydroxyl, or fluoroalkyl, and r is an integer from about 5 to about 700. Preferably, the F monomer has a general formula selected from the group consisting of the following, where m is 1, 2 or 3, p is zero or 1, R" may be alkyl or hydrogen, and X, R, and Z are as defined above: X-C-O-CCH,)— (O)-Si(R)j_ m Z m wherein q is an integer from 2 to 6; wherein q is an integer from zero to 2; H O R" X-C-O-CH 2 -CHz-N-C-N—(CH,)q-Si(R) 3 _ m zm wherein q is an integer from 2 to 6; and wherein q is an integer from 2 to 6. Y is a divalent linking group. R comprises hydrogen, lower alkyl groups such as methyl, ethyl, or propyl, aryl groups such as phenyl or substituted phenyl and alkoxy groups such as methoxy and ethoxy groups. Z is a monovalent siloxane polymeric moiety having a number average molecular weight above about 1,000 and is essentially unreactive under copolymerization conditions. The release agent of the present invention may comprise the copolymers of the two embodiments alone, or may comprise copolymers blended with other compatible homopolymers and/or copolymers. The low percentage of silicone contained in the copolymers makes the copolymers readily compatible with polymers of similar composition to vinyl polymeric blocks or segments. In addition, there are several pairs of dissimilar polymers that yield compatible blends due to specific interaction as described by S. Krause in Polymer Blends. Academic Press, New York, 1978. Introduction of a low level or silicone block onto one of these polymers will not influence compatibility. In addition, additives, fillers or pigments such as alumina, silica, titanate, or calcium carbonate may, of course, be added to the copolymer compositions. The release compositions do not require curing or crosslinking; however, if solvent resistance is desired for a particular application, crosslinking can be effected by standard methods well-known in the art, such as radiation curing (electron beam or ultraviolet light) or chemical crosslinking. The release agent should have a surface release value not greater than about 10 oz./in. (11 N/dm). Preferably, it should be not greater than 5oz./in. (5.5N/dm). It should be understood that this upper limit applies to use with highly aggressive repositionable pressure-sensitive adhesives. The release agent compositions may be applied to any substrate by means of conventional coating techniques such as wire-wound rod, direct gravure, offset gravure, reverse roll, air-knife and trailing blade coating. Suitable substrates include paper, non- woven fabrics and films of thermoplastic resins such as polyesters, polyamides, polyolefins, polycarbonates and polyvinyl chloride. Similarly, the adhesive compositions can be applied to a substrate by means of conventional coating techniques such as wire-wound rod, direct gravure, offset gravure, reverse roll, air-knife, spray coat, dye coat and trailing blade coating. Suitable backing or substrate materials for the adhesive composition include, but are not limited to, paper, plastic films, cellulose acetate, ethyl cellulose, woven or nonwoven fabric formed of synthetic or natural materials, metal, metallized polymeric film, ceramic sheet material and the like. The binder of the present invention should comprise a sufficient amount of at least one acrylamide-based moiety to limit interaction with the release agent of the present invention thereby permiting the repositionable high peel adhesion adhesive of the present invention to be removable from the release agent of the present invention. Moreover, once the adhesive composition is removed from the release agent, the adhesive composition should still maintain high peel adhesion and not build adhesion excessively over time. Likewise, the release agent should provide low sheet removal force while retaining indicia receptivity. The following examples are illustrative in nature and are not intended to limit the invention in any way. TEST METHODS PEEL ADHESION Peel adhesion is the force required to remove polyester film applied to the adhesive coated test material measured at a specific angle and rate of removal. In the examples, this force is expressed in grams per 1.25 inch width of coated sheet. The procedure followed is: A strip, 1.25 inches wide, of polyester film is applied to the horizontal surface of a adhesive coated sample fixed on a test plate. A 4.5 lb. hard rubber roller is used to apply the strip. The free end of the polyester film is attached to the adhesion tester load cell so that the angle of removal will be 90 degrees. The test plate is then clamped in the jaws of the tensile testing machine which is capable of moving the plate away from the load cell at a constant rate of 12 inches per minute. A load cell reading in grams per 1.25 inches of coated strip is recorded as the polyester film is peeled from the coated samples. SHEET REMOVAL FORCE Sheet removal force is the force required to remove a sheet from a stack of at least two sheets which are dimensioned one inch by five inches at a ninety angle and rate of removal of 12 inches per minute. In the examples, this force is expressed in grams per inch width of coated sheet. The procedure to determine the sheet removal force is: A strip of at least one inch wide double coated Scotch™ Brand 410 Tape commercially available from the Minnesota Mining and Manufacturing Company is adhered to a steel test plate. Thereafter, a one inch wide sample coated with adhesive is cut from the sheet is placed on the test plate, adhesive side down onto the tape so that the entire adhesive coated side of the test sample is covered. The test sample is placed parallel to the dimension of the test plate and the adhesive strip is centered so that the peel removal is made at a ninety degree angle. The test plate is then clamped in the lower jaws of Instron Tensile Tester which is capable of moving the plate away from the load cell at at rate of twelve inches per minute. A piece of Scotch™ Brand 810 Magic Tape commercially available from the Minnesota Mining and Manufacturing Company is then attached to the loose end of the top sheet. The tape is centered over the one inch loose end of the test sample. The free end of the tape is then clamped into the upper jaw of Instron Tensile Tester and then the sample is pulled away at a ninety degree angle and sheet removal force is measured. Test Samples Release Agent A A release agent of the present invention was made in the following manner: Fourty-five grams of methyl acrylate, 35 grams of N-vinyl pyrrolidone, 5 grams acrylic acid, 15 grams of mercapto functional available commericially available as KF-2001 from Shin-Etsu, 0.25 grams of Vazo™ 64 and 150 grams of methyl ethyl ketone were mixed together in a 16 oz. amber bottle. The mixture was purged with nitrogen for five minutes at one liter per minute and then the bottle was sealed and tumbled in a constant temperature bath at 55° C for 48 hours. The conversion was 98 percent. Release Agent B A release agent of the present invention was made in the following manner: Ninety-seven and eight tenths grams of methyl acrylate, 76.1 grams of N-vinyl pyrrolidone, 10.9 grams of acrylic acid, 65.2 grams of the polymeric vinyl- terminated monomer F prepared in accordance with the procedures described in U.S. Patent No. 4,728,571, 0.625 grams of Vazo™ 64 and 375 grams of methyl ethyl ketone were mixed in a 32 ounce amber bottle. The mixture was purged with nitrogen for five minutes at one liter per minute and then the bottle was sealed and tumbled in a constant temperature bath at 55° C for 48 hours. The conversion was 99.2 percent. Microspheres The microspheres of the present invention were made in the following manner: At room temperature, 307.69 grams of distilled water, 2.05 grams of ammonium lauryl sulfateand 2.56 grams of Acrylic Acid were added to the mixture. This mixture was neutralized by adding a sufficient amount of ammonium hydroxide to achieve a pH level of 7.0. This mixture was then heated to 70°C. 100 grams of Iso-octyl acrylate and 0.31 grams of Benzoy1 Peroxide were then added to this solution. Together, this mixture is rapidly stirred with an agitation rate to yield sufficient particle size. The reaction is then cooled to about 65°C until the reaction exotherms. After exotherm temperature is reached, the mixture is cooled for 7 hours at 60°C for seven hours. The solution is then filtered and allowed to separate into two layers. The top layer is then coagulated with isopropyl alcohol. The alcohol is extracted and the microspheres are redispersed in heptane. Binder The adhesive binder was prepared in the following manner: 155.61 grams of Ethyl Acetate, 100 grams of Iso¬ octyl Acrylate and 4.15 grams of acrylamide, 0.22 grams of benzoyl peroxide and 180.57 grams of heptane. The mixture was heated at 59° C for 48 hours. Thereafter, 0.66 grams of ethyl acetate and 0.49 grams of Santanox were added. Example 1 Using a 60 pyramidal gravure cylinder, the 15% solids Release Agent A was applied to virgin white paper commercially available from Crosspointe Paper Company of Miami Mill, Carrolton, Ohio. Equal amounts of 23% solids of the micropheres and 23% solids of the adhesive binder described were coated at about 140 grams per inch wet adhesive in a two inch width pattern parallel to the edge and one half inch from the edge. The peel adhesion for the adhesive composition was 300 grams/1.25 inch. The sheet removal force is approximately 20 grams/1 inch. The paper was sheeted into a pad form to be used as a flipchart with the ability to flip pages easily, remove sheets with no curl and hang on a variety of office wall surfaces for up to 48 hours. Example 2 Using a 120 ruling mill gravure cylinder, a 15% solids Release Agent A was applied to virgin white paper commercially available from Crosspointe Paper Company of Miami Mill. A blend of equal amounts of 23% solids microspheres and 23% solids adhesive binder were coated in two 1 inch strips parallel. The strips were coated 21 inches apart from each other. The adhesive blend was coated at about 140 grams per inch wet adhesive. The peel adhesion was measured to be 300 grams/1.25 inch. The sheet removal force was approximately 40 grams/l inch. In summary, novel adhesive systems have been described. Although specific embodiments and examples have been disclosed herein, it should be borne in mind that these have been provided by way of explanation and illustration and the present invention is not limited thereby. Certainly, modifications which are within the ordinary skill in the art are considered to lie within the scope of this invention as defined by the following claims including all equivalents.

Claims: We Claim : 1. A system comprising: a. a release agent comprising a polymer having at least one vinyl polymeric segment having a T g between -10°C and 65°C and at least one siloxane polymeric segment; and b. a high peel adhesion repositionable adhesive composition comprising a blend of one or more polymeric and elastomeric microspheres and an adhesive binder comprising a sufficient amount of at least one acrylamide-based moiety to limit interaction of said adhesive composition with said release agent. 2. The adhesive system of Claim 1 wherein said binder further comprises at one free radical polymerizable monomer copolymerized with said acrylamide-based moiety. 3. The system of Claim 2 wherein said free radical polymerizable monomer is selected from the group consisting of an acrylate or methacrylate. 4. The system of Claim 1 wherein said composition comprises from about 10 to about 90 parts by weight of said binder and from about 90 to about 10 parts by weight of said microsphere. 5. The system of Claim 1 wherein said release agent is a copolymer comprising the formula: wherein R, are monovalent moieties which can independently be the same or different and are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fluoroalkyl; R 2 can independently be the same or different and are divalent linking groups; R 3 are monovalent moieties which can independently be the same or different and are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fluoroalkyl; R 4 can independently be the same or different and are divalent linking groups; x is an integer of 0-3; y is an integer of 10 or greater; q is an integer of 0-3;; and G 5 are monovalent moieties which can independently be the same or different selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoralkyl, hydrogen, and -WSA; A is a vinyl polymeric segment or block consisting essentially of polymerized free radically polymerized monomer selected from the consisting of N-vinyl pyrrolidone, N,N-diethylaminoethyl methacrylate, N,N- dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate and N-t- butylamino ethyl methacrylate, styrene, methyl methacrylate, methyl acrylate, acrylic acid, itaconic acid, maleic acid, 2-carboxy ethyl acrylate, acrylamide, methacrylamide, aerylonitrile, isobornyl methacrylate, butyl methacrylate, isopropyl methacrylate, vinyl acetate, hydroxy propylacrylate, hydroxy ethyl acrylate, dihydroxy propyl acrylate and mixtures thereof; G 6 are monovalent moieties which can independently be the same or different selected from the group consisting of alkyl, aryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -ZWA; and G 2 and G 4 comprise A. 6. The release agent of Claim 1 wherein said polymer is a copolymer of D and E monomers copolymerized to form a polymeric backbone with F monomer grafted thereto wherein: D is at least one free radically polymerizable vinyl monomer; E is at least one polar monomer copolymerizable with D, the amount of E being up to 30% of the total weight of all monomers, and F is a monomer having the general formula X-(Y) n SiR (3 . m) Z m wherein X is a vinyl group copolymerizable with the D and E monomers, Y is a divalent linking group where n is zero or 1; m is an integer of from 1 to 3; R is hydrogen, lower alkyl (e.g., methyl, ethyl, or propyl) , aryl (e.g., phenyl or substituted phenyl) , or alkoxy; and Z is a monovalent siloxane polymeric moiety having a number average molecular weight above about 1,000 and is essentially unreactive under copolymerization conditions. 7. The release agent of Claim 6 wherein said D monomer is selected from the group consisting of styrene, vinyl acetate, vinyl chloride, vinylidene chloride, aerylonitrile, acrylic or methacrylic acid esters of non-tertiary alcohols having from 1 to about 18 carbon atoms and mixtures thereof. 8. The release agent of Claim 7 wherein said E monomer is selected from the group consisting of N- vinyl pyrrolidone, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N- diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate and N-t-butylamino ethyl methacrylate, styrene, methyl methacrylate, methyl acrylate, acrylic acid, itaconic acid, maleic acid, 2-carboxy ethyl acrylate, acrylamide, methacrylamide, acrylonitrile, isobornyl methacrylate, butyl methacrylate, isopropyl methacrylate, vinyl acetate, hydroxy propylacrylate, hydroxy ethyl acrylate, dihydroxy propyl acrylate and mixtures thereof. 9. An article comprising at least a first and a second substrate, said first substrate having a rear surface coated with a high peel, repositionable adhesive composition comprising a blend of a polymeric and elastomeric microspheres and a binder containing at least one acrylamide moiety and said second substrate having at least a portion of said front surface coated with a release agent comprising a polymer having at least one vinyl polymeric segment having a T g between - 10°C and 65°C and at least one siloxane polymeric segment. 10. The article of Claim 9 wherein said article further comprises at least one substrate therebetween said first and second substrates, each additional substrate having a front and a rear surface, said front and rear surfaces of said additional substrates facing each other, each additional substrate having at least a portion of a said rear surface coated with said adhesive composition and at least a portion of each said front face with said polymer.

Inventors: BILSKI LORI A, KUMAR RAMESH C, MERTENS TIMOTHY A, WILSON SHARI J, BILSKI, LORI, A., KUMAR, RAMESH, C., MERTENS, TIMOTHY, A., WILSON, SHARI, J.
Applicants: MINNESOTA MINING & MFG, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1994
Main classification: C09J7
IPC codes: C08F283, C09D151, C09J7, C09J151, C09J157, C09J183, C09J201